Silver-Catalyzed Cascade Radical Bicyclization Reaction: An Atom- and Step-Economical Strategy Accessing γ-Lactam Containing Isoquinolinediones.

An efficient and convenient method for the cascade radical bicyclization of N-phenyl-4-pentenamides with N-methyl-N-methacryloylbenzamides under silver-catalyzed conditions is described. Based on this newly developed strategy, a variety of valuable γ-lactam containing isoquinolinediones can be effectively synthesized in one step within 0.5 h, during which two C-C bonds, one C-N bond, and two new N-heterocycles were formed concurrently. With N-aryl allyl carbamates, similar 2-oxazolidinone substituted isoquinolinedione compounds can likewise be produced. The approach demonstrates wide functional group compatibility, high step- and atom-economy, and the ability to be scaled up to gram quantities in a satisfactory yield. It marks the first instance of introducing γ-lactams into isoquinoline-1,3(2H,4H)-diones to construct linked hybrid drug-like molecules, thereby making this strategy highly attractive to drug discovery.

Synthesis of cyano-substituted γ-lactams through a copper-catalyzed cascade cyclization/cyanation reaction.

A convenient copper-catalyzed cascade cyclization/cyanation reaction for the construction of cyano-containing γ-lactams was developed. The protocol employed TMSCN as the cyano source and proceeded in water under simple conditions. Mechanistic studies indicated this reaction involved an amidyl radical initiated cascade 5-exo-trig cyclization/cyanation process. It is capable of generating a series of cyano-substituted γ-lactams and relative 2-oxazolidinone derivatives with a broad substrate scope.

Silver-catalyzed cascade cyclization and functionalization of N-aryl-4-pentenamides: an efficient route to γ-lactam-substituted quinone derivatives.

The synthesis of γ-lactam-substituted quinone derivatives through a Ag2O-catalyzed cascade cyclization and functionalization of N-aryl-4-pentenamides has been developed. Related 2-oxazolidinone substituted quinone products can be also obtained with N-aryl allyl carbamates. The reactions proceed through an amidyl radical-initiated 5-exo-trig cyclization and followed radical addition to quinones. They provide an efficient route to various γ-lactam-substituted quinone derivatives with a wide range of substrate scope.

Synthesis of organic liquid crystals containing selectively fluorinated cyclopropanes.

This paper describes the synthesis of a series of organic liquid crystals (LCs) containing selectively fluorinated cyclopropanes at their termini. The syntheses used difluorocarbene additions to olefin precursors, an approach which proved straightforward such that these liquid crystal candidates could be efficiently prepared. Their physical and thermodynamic properties were evaluated and depending on individual structures, they either displayed positive or negative dielectric anisotropy. The study gives some guidance into effective structure-property relationships for the design of LCs containing selectively fluorinated cyclopropane motifs.

Unexpected α,α'-difluoroethers from Ag(i)F and N-bromosuccinimide reactions of dibenzo[a,e]cyclooctatetraene.

An unexpected and highly efficient reaction of dibenzo[a,e]cyclooctatetraene with Ag(i)F and N-bromosuccinamide in dichloromethane results in a sequential ring contraction pathway to generate bridged bicyclic α,α'-difluoroether isomers 10 and 11 where the ether oxygen is isotopically labelled from oxygen-18 water. In diethyl ether the same reaction generates the more classical vicinal difluoride isomers 13 and 14.

Fluorine containing cyclopropanes: synthesis of aryl substituted all-cis 1,2,3-trifluorocyclopropanes, a facially polar motif.

The syntheses of substituted all-cis-1,2,3-trifluorocyclopropanes are described for the first time. The three fluorines located on each of the cyclopropyl carbons with a stereochemistry where they are all on the same face of the cyclopropane, imparts a significant polarity to the molecule, and the inherent conformational rigidity and lowering of log P makes this motif attractive for exploration as a substituent for pharmaceuticals and agrochemicals research.

Polar alicyclic rings: synthesis and structure of all cis-1,2,3,4-tetrafluorocyclopentane.

The all-cis isomer of 1,2,3,4-tetrafluorocyclopentane is prepared and characterised by NMR and X-ray crystallography and the experimental structure compared with theory. The structure has a similarly high polarity to all-cis tetrafluorocyclohexanes despite the increased conformational flexibility of a cyclopentane.

Formation and characterization of silver nanoparticles in aqueous solution via ultrasonic irradiation.

In this study, a simple and green method to synthesize silver nanoparticles (Ag NPs) in aqueous solution via ultrasonic irradiation has been developed. Ultrafine Ag NPs with average diameter of 8 nm were obtained through sonicating aqueous solution of sodium hydroxide (NaOH, 0.1 mM) with adding silver nitrate solution (AgNO3, 5.88 mM) drop by drop. In pure aqueous solution, the reactive route related to hydroxyl radicals (OH) is presented. Furthermore, in alkaline aqueous solution, the effects of hydroxyl ions (OH(-)) on formation of Ag NPs are discussed detailedly. The formation of Ag NPs was tracked by surface plasmon resonance (SPR) band of ultraviolet-visible (UV-Vis) spectrum; the morphology of the obtained Ag NPs was characterized through transmission electron microscopy (TEM); energy dispersive X-ray spectroscopy (EDX) and X-ray powder diffraction (XRD) confirmed the formation of metallic Ag NPs.